PCL-b

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Sequential crystallization and morphology of triple crystalline biodegradable PEO-

b-PCL-b-PLLA triblock terpolymers

Item Type Article

Authors Palacios, Jordana;Mugica, Agurtzane;Zubitur, Manuela;Iturrospe, Amaia;Arbe, A.;Liu, Guoming;Wang, Dujin;Zhao,

Junpeng;Hadjichristidis, Nikos;Muller, Alejandro

Citation Sequential crystallization and morphology of triple crystalline biodegradable PEO-b-PCL-b-PLLA triblock terpolymers 2016 RSC Adv.

Eprint version Post-print

DOI 10.1039/C5RA25812J

Publisher Royal Society of Chemistry (RSC)

Journal RSC Advances

Rights Archived with thanks to RSC Adv.

Download date 2023-12-13 18:11:22

Link to Item http://hdl.handle.net/10754/593139

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1

ELECTRONIC SUPPLEMENTARY INFORMATION

Sequential crystallization and morphology of triple crystalline biodegradable PEO-b- PCL-b-PLLA triblock terpolymers

Jordana K. Palacios

¹

, Agurtzane Mugica

¹

, Manuela Zubitur

²

, Amaia Iturrospe

³

, Arantxa Arbe

³

, Guoming Liu

⁴

, Dujin Wang

⁴

, Junpeng Zhao

⁵

, Nikos Hadjichristidis*

⁵

and

Alejandro J. Müller*

^1,6

1

POLYMAT and Polymer Science and Technology Department, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizabal 3, 20018

Donostia-San Sebastián, Spain.

2

Chemical and Environmental Engineering Department, Polytechnic School, University of the Basque Country UPV/EHU, 20018 Donostia-San Sebastián, Spain

3

Materials Physics Center (CSIC-UPV/EHU), Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastián, Spain.

4

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.

5

King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering Division, KAUST Catalysis Center, Thuwal, Saudi Arabia

6

IKERBASQUE, Basque Foundation for Science, Bilbao, Spain.

*corresponding authors: [email protected] and [email protected]

Electronic Supplementary Material (ESI) for RSC Advances.

This journal is © The Royal Society of Chemistry 2016

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S1. Differential scanning calorimetry (DSC)

Several tests, at different cooling rates, were carried out to establish the ideal rate to achieve the crystallization of the blocks.

0 50 100 150

0 50 100150

2 m W

CR = 1 ºC min

^-1

HR = 20 ºC min

^-1

CR = 2.5 ºC min

^-1

HR = 20 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

E nd o H ea t f lo w (m W )

Temperature (°C)

a)

0. 2 m W

PEO29PCL42PLLA29 16.1

0 50 100 150

5 m W

PEO29PCL42PLLA29 16.1 b)

CR = 1 ºC min

^-1

HR = 20 ºC min

^-1

Temperature (°C)

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3

0 50 100 150

a)

2 m W E nd o PEO29PCL42PLLA29 16.1

CR = 1 ºC min

^-1

HR = 1 ºC min

^-1

CR = 5 ºC min

^-1

HR = 5 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

H ea t f lo w (m W )

Temperature (°C)

0 50 100 150

b)

5 m W

CR = 1 ºC min

^-1

HR = 1 ºC min

^-1

CR = 5 ºC min

^-1

HR = 5 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

Temperature (°C)

Figure SI.2. a) DSC cooling scans at several cooling rates (CR) after melting at 160 ºC for 3 min and b) Subsequent DSC heating scans at several heating rates (HR) for PEO₂₉PCL₄₂PLLA₂₉^16.1.

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0 50 100 150 0 50 100 150

a)

0. 2 m W

CR = 1 ºC min

^-1

HR = 20 ºC min

^-1

CR = 2.5 ºC min

^-1

HR = 20 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

Temperature (°C)

0 50 100 150

b)

1 m W

CR = 1 ºC min

^-1

HR = 20 ºC min

^-1

CR = 2.5 ºC min

^-1

HR = 20 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

Temperature (°C)

Figure SI.3. a) DSC cooling scans at several cooling rates (CR) after melting at 160 ºC for 3 min and b) Subsequent

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5

0 50 100 150

a)

CR = 1 ºC min

^-1

HR = 1 ºC min

^-1

CR = 5 ºC min

^-1

HR = 5 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

Temperature (°C)

0 50 100 150

b)

1 m W

CR = 1 ºC min

^-1

HR = 1 ºC min

^-1

CR = 5 ºC min

^-1

HR = 5 ºC min

^-1

CR = 20 ºC min

^-1

HR = 20 ºC min

^-1

Temperature (°C)

Figure SI.4. a) DSC cooling scans at several cooling rates (CR) after melting at 160 ºC for 3 min and b) Subsequent DSC heating scans at several heating rates (HR) for PEO₂₃PCL₃₄PLLA₄₃^19.9.

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S2. DSC Thermal properties of the triblock terpolymers studied here and some diblock and triblock copolymers reported in the literature.

In Table S.1 are included the DSC thermal properties of the triblock terplymers and compared to relevant block copolymers previously reported.

Table S.1. Crystallization and melting temperatures of PEO29PCL42PLLA2916.1and PEO23PCL34PLLA4319.9 triblocks terpolymers compared to different linear diblock copolymers reported in the literature

PLLA PCL PEO

Sample code Block M_w (kg mol^-1)

T_c (ºC)

T_m (ºC)

Block M_w (kg mol^-1)

T_c (ºC)

T_m (ºC)

Block M_w (kg mol^-1)

T_c (ºC)

T_m (ºC)

Ref.

PEO29PCL42PLLA2916.1 4.7 75.0 124.5 6.8 41.7 56.9 4.6 33.5 48.0

PEO₂₃PCL₃₄PLLA₄₃^19.9 8.5 72.3 121.8 6.8 36.7 54.2 4.6 22.1 45.0

Samples reported here

L93C718 15.7 102.6 171.7 1.7

L₈₁C₁₉²¹ 16.7 102.8 170.5 3.9

L₆₀C₄₀²¹ 12.4 102.8 168.9 8.5 0.5-

11.3 54.4

L55C4518 9.5 98.3 166.9 8.1 20.8 55.0

L₄₄C₅₆²⁵ 11.1 91.8 166.5 14.2 23.2 56.5

L32C6822 6.9 100.3 161.0 14.9 28.1 56.9

L10C9024 2.4 86.8 141.5 21.5 32.5 57.7

Castillo, 2010²

PLLA2300bPEG5000 2.3 93.0 140.1 5.0 34.1 54.7

PLLA6300bPEG5000 6.3 105.2 153.8 5.0 34.6 42.2

PLLA12000bPEG5000 12.0 116.3 162.4 5.0 12.9 37.2

Sun, 2004¹

PEO5-b-PLLA16 16.0 90.6 141.2 5.0 41.2

PEO₅-b-PLLA₃₀ 30.0 100.0 142.1 5.0 39.7 Huang,2008³

2LPCL50-b-PLLA43 12.45 102.4 151.7 11.33 12.6 51.2 Wang,2006⁵

PEOCL56 6.24 30.4 55.4 5.0 30.4 55.4

PEOCL62 8.13 34.3 56.3 5.0 28.7 56.3 He, 2006⁶

PEG5000-PCL1000 1.0 5.0 34.7 59.8

PEG5000-PCL2900 2.9 5.0 30.0 51.0/5

4.9

PEG5000-PCL9200 9.2 34.6 56.7 5.0 29.3 44.6

Sun, 2011⁷

PCL13-PEG45-PCL13 3.0 16.5 51.7 2.0 12.2 41.2 Wei, 2009⁸

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7 References of supporting information

(1) Sun, J.; Hong, Z.; Yang, L.; Tang, Z.; Chen, X.; Jing, X. Polymer 2004, 45, 5969-5977.

(2) Castillo, R. V.; Müller, A. J.; Raquez, J. M.; Dubois, P. Macromolecules 2010, 43, 4149-4160.

(3) Huang, S.; Jiang, S.; An, L.; Chen, X. J. Polym. Sci., Part B: Polym. Phys. 2008, 46, 1400-1411.

(4) Muller, A. J.; Avila, M.; Saenz, G.; Salazar, J. In Poly(Lactic Acid) Science and Technology: Processing, Properties, Additives and Applications, Jimenez, A.,Peltzer, M.,Ruseckaite, R., Eds.; The Royal Society of Chemistry: Cambridge, 2015; Chapter 3, p 66.

(5) Wang, J. L.; Dong, C. M. Macromol. Chem. Phys. 2006, 207, 554-562.

(6) He, C.; Sun, J.; Ma, J.; Chen, X.; Jing, X. Biomacromolecules 2006, 7, 3482-3489.

(7) Sun, J.; He, C.; Zhuang, X.; Jing, X.; Chen, X. J. Polym. Res. 2011, 18, 2161-2168.

(8) Wei, Z.; Liu, L.; Yu, F.; Wang, P.; Qi, M. J. Appl. Polym. Sci. 2009, 111, 429-436."

S3. Polarized light optical microscopy (PLOM). Photographs videos

PLOM was performed on cooling from the melt in order to observe the sequential crystallization and superstructure formation of each block. Small videos made of PLOM photograps for each triblock terpolymer are presented.

TriblockTerpolymer 16.1.ppsx TribloqueTerpolymer 16.1.ppsx TriblockTerpolymer 19.9.ppsx TriblockTerpolymer 19.9.ppsx